DE1646818B1 - Piezoelectric ceramic material - Google Patents

Description

t 646 818

1 ^: 2

The invention relates to piezoelectric ceramic niche advancement. In practice, however, the material that contains lead titanate (PbTiO ₃ ) and / or lead-zir quality and usability of a ceramic material is conat (PbZrO ₃ ). In particular, the invention relates to other variables in determining new piezoelectric ceramics, which are sufficient, especially the dielectric constant,
have drawn properties and for use 5 The invention is based on the object of new

are suitable in special areas. specify piezoelectric ceramics that have a large

One of the typical areas of application piezo-ben have electromechanical coupling factor, electrical materials is the manufacture of wall and especially for use on special gels for the transmission and reception of ultra-offers, for example for the production of converters Sound waves. In this case the electromechanical io for the transmission and reception of ultrasonic coupling factor the essential measure for the beur waves, are suitable.

division of the properties of the piezoelectric to be used The piezoelectric created by the invention

electrical materials in practice. The electrome- see ceramic material, the lead titanate and / or

mechanical coupling factor characterizes the active lead zirconate contains, consists essentially of one

ability to convert electrical vibrations 15 solid solution of the components

into mechanical and vice versa of conversion.

mechanical vibrations in electrical oscillations- ^Fb ^^ / s ^ a / sMb VbLiV ₃ unü J ^ bZrU ₃

gen, where larger values of the coupling factor are where Z is the elements niobium (Nb) and / or antimony

indicate better conversion efficiency and (Sb) represents.

for piezoelectric materials that are used in the manufacture of ao It should be noted in advance to Tables 1 and

ment of transducers are desired 2 referenced. The highest there for ceramic material

are. according to the invention for the coupling factor

Piezoelectric materials have some other values given according to Table 1 for the pro-basic factors, such as: B. the dielectric verbs 14 and 17 68 or 66% and according to Table 2 for the loss factor, the dielectric constant and the 25 the samples 10 and 11 77% to assess the materials used in the above-mentioned article. In certain transducer for piezoelectric listed CSAR by Br K u 1, 57% Is ^a material is a low dielectric loss factor - high coupling factor is called. In addition, if desired, the desired value of the dielectric constant in ceramics according to the invention nor the high constant can be large or small depending on the values of the dielectric constant in spite of the high coupling of the electrical load, during the mechanical. factors. They are for samples 14 and 17 figure of merit is not particularly important. of Table 1, for example, 1695 or 1600. Such

The above information is described in detail, for example, in high values of the dielectric constants occur in the following literature references: D. Berlin- the known compositions according to the gec ο urt et al., Transducer Properties of Lead Titanate 35 named article only in connection with low zirconate cramics, » IRE TRANSACTIONS ON UL coupling factors of 50% and less.
TRASONIC ENGINEERING ", February, 1960, p. 1 It is advantageous if the material has essentially up to 6, and RCV M acario," Design Data for a composition that is determined by the formula Band-Pass Ladder Filters Employing Ceramic Resonators ", ELECTRONIC ENGINEERING, Vol. 33, 40 (Pb (Fe ₁ Z ₃ Z ₂ Z ₃ ) O ₃ ) ^ (PbTiOg) ₂ , (PbZrO ₃ ) _z
No. 2 (1961), pp. 171 to 177.

As a rule, however, the usual ones have been given, where Z is one of the elements niobium (Nb) or

piezoelectric ceramics, for example barium antimony (Sb) and x, y and ζ molar fractions

titanate - BaTiO ₃ - and lead-titanate-zirconate, the sum of which is 1.0, the amounts of which in the following

- Pb (TiZr) O ₃ -, a low electromechanical 45 the limits of the three-component system of the three components

Coupling factor and are for practical use: χ = 0.01 to 0.5, y = 0.00 to 0.75,

unsuitable. Improvements in this factor were ζ = 0.15 to 0.90.

The present invention is based on the new acquisition parts reached into the ceramic material. knowledge that ceramic compounds produced in

Thus, in the Journal of The American Cera- 50, there is essentially a solid solution to the ternary

mic Society ", Vol. 42, No. 7 (July 1959), in the essay Systems

by Ms. KuI es ar »Electromechanical Properties Pb (Fe ₁ Z ₃ Z ₂ Z ₃ ) O ₃ -PbTiO ₃ -PbZrO ₃
of Lead Titanate Zirconate Ceramics Modified with

Certain Three- or Five-Valent Additions «in the Ta- consist, where Z is one of the elements niobium (Nb) and

bellen I and II on p. 344 represents piezoelectric values for 55 antimony (Sb), excellent piezoelectric

Compositions that show a whole range of activities and thus practical importance

have various additives to the basic ingredient. The ceramic compounds mentioned contain

,. . . Lead (Pb) as a divalent metallic element and

^ f (Zr ₅₄ 4lio, 46; 0 ₃ also titanium (Ti) and zirconium (Zr) as tetravalent

contain. The highest coupling factor listed is 60 metallic elements. In addition, the egg

is 0.57 or 57%. It is the sample B-12 of the element iron (Fe) and one of the elements niobium (Nb)

belle II own, in which the additives _{contain Nb 2} O ₅ and La ₂ O ₃ and antimony (Sb) in such an amount that

are. they taken together essentially a four-

The maximum Kopp-valued metallic elements, which can only be understood theoretically, are equivalent,
The coupling factor is 100% · It is extremely difficult to create 65 In the case that niobium (Nb) is chosen for Z and that a ceramic material, which is a coupling agent, the ceramic material of the ternary system
factor reached above 60%. Exceeding this limit already means a considerable amount of tech- Pb (Fe ₁ Z ₃ Nb ₂ Z ₃ ) O ₃ -PbTiO ₃ -PbZrO ₃

is represented by the formulaic composition

(Pb (Fe ₁ Z ₃ Nb ₂ Z ₃ ) O ₃ MPbTiO ₃ MPbZrO ₃ ) *

where x, y or ζ indicates the molar fraction of each component and χ + y + ζ = 1.00, it was found that the compounds with regard to their effective properties can be related to a range given by the following ratios of the molar fractions:

X y Z 0.01 0.55 0.44 0.01 0.09 0.90 0.10 O ₃ OO 0.90 0.40 0.00 0.60 0.50 0.10 0.40 0.50 0.30; 0.20 0.20 0.65 0.15 0.10 0.75 0.15 0.05 0.75 0.20

Likewise, when antimony (Sb) is chosen for Z, the effective range of ceramic compounds is the by the formula

(Pb (Fe ₁ Z ₃ Sb ₂ Z ₃ ) O ₃ ) S (PbTiO ₃ ) ^ (PbZrO ₃ ) *

are given, where χ + y + ζ - 1.00, determined by the following ratios of the molar fractions x, y and ζ :

X y Z 0.01 0.55 0.44 0.01 0.09 0.90 0.10 0.00 0.90 0.40 0.00 0.60 0.40 0.40 0.20 0.05 0.75 0.20

If you take the first of the three listed components of the piezoelectric ceramic material according to the invention niobium (Nb) for Z, so one has with

a connection before you, that of the one in the journal "Soviet Physical Solid State", 1959, in the article by G. A. Smolenskii and A. I. Agranovs k a y a "Dielectric Polarization of a Number of Complex Compounds ”on p. 1432

Pb (Fe ₁ Z ₂ Nb ₁ Z ₂ ) O ₃

may appear similar. It will be shown below that due to different proportions of There are considerable differences between elements between otherwise identical connections, using the example

Pb (Fe ₁ Z ₂ Sb ₁ Z ₂ ) O ₃ and Pb (Fe _{l / 3} Sb _{l / 3} ) O ₃

In the article mentioned, only the possibility of the existence of

Pb (Fe ₁ Z ₂ Nb ₁ Z ₂ ) O ₃

ίο explains, but not the possibility of the existence of one ternary system in the form of a solid solution with this compound or compound

Pb (Fe ₁ Z ₃ Nb ₁ Z ₃ ) O ₃

as the first component and PbTiO ₃ and PbZrO ₃ as the second or third component, as represented by the material according to the invention. Since the essay does not even treat these ternary systems as such! there is also no indication that

so assumed they have piezoelectric properties superior to those of known compositions.

This is also clear from Table 4 on p. 1433 of the article, which shows the behavior of ε and tan δ for a large number of complex compounds. According to various compounds, ε changes from 22 to 9000 and tan δ from 0.001 to 0.54. The compounds can not be seen under the same light therefore for their ε- and tan δ- values. the

Piezoelectric properties not only of the compounds known from the article but also of the compounds according to the invention cannot be predicted on the basis of the values for ε and tan δ and their spontaneous polarization.

The inventors of the piezoelectric ceramic material discussed here almost at the same time in Shape of

Pb (Fe ₁ Z ₂ Sb ₁ Z ₂ ) O ₃ -PbTiO ₃ -PbZrO ₃

a composition proposed (German patent application P 16 46 819.2-45), which also brought a considerable improvement in the electromechanical coupling factor compared to that of the ceramics known at the time. It differs from the one alternative for ceramic material according to the invention - Sb for Z - only by the mixing ratio "of Fe and Sb after another proposal is 1: 2: 1, the ceramic material according to the invention, but the first This difference is extremely significant. It is based on; the use of Fe as a trivalent metal in the connection according to the other proposal, on the other hand as a divalent metal in the material according to the invention. The following overview makes this clear, except for the coupling factor k _r for the mechanical quality factor Q _m , the dielectric constant ε and the dielectric loss angle tan δ .

OC. 68
77 Sqm ε tan δ Compositions according to the other proposal V ₂
Va 290
83 880
1480 1.8
2.8 Compositions according to the invention

The values in this overview apply to χ - 0.05, 65 according to the requirements of the application, y = 0.46 and ζ = 0.49. Compositions according to his

It can be seen that the factors are very different from finding or those according to dsm parallel to this, depending on whether α = ¹ J ₂ or ¹ J ₅ . Choose the th suggestion.

5 6

Among the usual piezoelectric ceramics, unless otherwise noted, a ceramic solid solution of the ternary system with a powdery form of lead oxide (PbO), iron (III) oxide (Fe ₂ O ₃ ), niobium (V) -

■ DUf \ / r XTU \ n. ηι.τ · Λ nw ^ ^οχ "* (Nb ₂ O), titanium dioxide (TiO ₂ ) and zirconium

Fb (Mg _{l / 3} JN b _2/3 ) O ₃ -Fb HO ₃ -PbZrO _{3 dioxM} ^ q ^ _used . _D i _ese materials in powder known, the loading in the USA. Patent 3,268,453 5 were measured out form so that the finished parts

is written. In this common ceramic material, the composition ratios shown in Table 1

rial, however, the piezoelectric properties could show nits. Likewise, as training

the well-known lead titanate-lead zirconate ceramics transition materials for the production of ceramics

not improved by itself, but a good formula

Piezoelectric material is only used by adding we- ίο you / t? » ei, \ η dut; a pkwo

. ,. Jy-VJ »τ Tr i. ii -nt · ι ι Jr D (re ^ a b ₂ z ₃ ju ₃ -Jr b ι iu ₃ -r dzju ₃

at least one of the oxides of manganese, cobalt, nickel,

Iron and chromium as additional constituents up to, unless otherwise noted, powder of lead (II) -3 percent by weight. In contrast to this are oxide (PbO), iron (III) oxide (Fe ₂ O ₃ ), antimony (III) - in the case of the compounds oxide (Sb ₂ O ₃ ), titanium dioxide (TiO ₂ ) and zirconium-

_pt _ _n ¹⁵ dioxide (ZrO ₂ ) used. These powders became like that too

Fb ^ e _{l / 3} z, _2/3 jU ₃ -FbliU ₃ -Fb /, ru ₃ measured that the end bodies have the composition ratios given in Table 2 according to the present invention, in which Z niobium. (Nb) or antimony (Sb), the piezoelectric iron oxide (Fe ₂ O ₃ ) and antimony (III) oxide (Sb ₂ O ₃ ) see properties by themselves (without any were weighed, each calculated on the basic additional ingredient ) remarkably improved, ao position of iron (II) oxide (FeO) and antimony (V) oxide This difference in the improvement of the piezoelec- (Sb ₂ O). Furthermore, the powders of lead monoxide, tric properties between the usual compound titanium dioxide and zirconium dioxide fertilize in such an amount and the new compounds according to the pre-weighed that the usual lead titanate-zirconate Keliegende invention is, so it is assumed, on ramiken of in The composition shown in Table 3 is attributable to the fact that the usual ratios were obtained.

bonds Magnesium (Mg), thus an element of the The respective powders were in ball mills with

Group IIA of the periodic table, mixed with distilled water. The mixed powders an element of group VB, namely niobium (Nb) were filtered, dried, crushed and then at containing, while in the compounds of the present- 900 ⁰ C for one hour and again the invention an element of group VIII, namely 30 crushed. Then the mixtures with iron (Fe), in connection with an element of the small amount of distilled water, which is added to group VB or VA, namely niobium (Nb) or anti, were made into disks of 20 mm in diameter with a mon (Sb) are included. Pressure of 700 kg / cm ² pressed and in an atmosphere

Excellent piezoelectric activities of the sphere of lead monoxide (PbO) during one hour. Ceramic compounds according to the invention are sintered at a temperature between 1260 and 1300 ° C. in the following, described in detail. However, for such bodies, the less preferred examples obtained were also in the drawing than 40 mole percent of
calculations are shown. Show in the drawings. , _Λ

F i g. 1 and 4 triangular diagrams of the ternary Sy- Pb (^ e ₁ Z ₃ JN b _2/3 ) O ₃

stems, being both the effective range of the 40 and 40 mole percent or more of the same bonds according to the invention as well as the individual contained (nos. 20, 25, 26, 29, 33 and 36 of the Tanen Compounds of the examples are shown, belle 1), specific temperatures of 1300 resp.

F i g. 2 and 5 are graphs of the electro-1270 ° C used in sintering. The resulting mechanical coupling factors of both the usual ceramic disks were polished (ground) on both surfaces of lead-titanate-zirconate ceramics and the ceramic to a thickness of 1 millimeter, according to the invention as a function of the joint on both surfaces Silver electrodes provide dimensional change of lead titanate and then piezoelectrically activated by a poly-lead zirconate in both ceramics and risations treatment at 100 ⁰ C for one hour

F i g. 3 and 6 phase diagrams of the ternary system with the application of an electrical direct current field stems of the present invention. 50 by 50 kV / cm.

The F i g. 1, 2 and 3 apply to the new ternary sy- For some bodies the polarization treatment has been

system, however, under different conditions

Pb (Fe ₁ Z ₃ Nb ₂ Z ₃ ) O ₃ -PbTiO ₃ -PbZrO ₃ out. In particular, DC electric fields of 40 and 30 kV / cm instead of 50 kV / cm were used for the ceramic compounds of this invention. ₅₅ applied, and in those bodies the more

The F i g. 4, 5 and 6 are valid for the new ternary _system-a i _s 30 mole percent but not more than 40 Molproste ¹¹¹ centrally of

Pb (Fe ₁ Z ₃ Sb ₂ Z ₃ ) O ₃ -PbTiO ₃ -PbZrO ₃ Pb (Fe _{l / 3} Nb ₂ , ₃ ) O ₃

of the ceramic compounds of this invention. _{5o (Nos.} 33 _{and 36 of Table 1) contained or for}

Examples of such bodies that are more than 40 mole percent of the same

components (Nos. 25, 26 and 29 of

Table 1) applies to the examples given in the table. The same was done for bodies that are more than the following production methods: 20 mol percent, but not more than 30 mol percent

As starting materials for the production of the 65 von =
Ceramics of the formula Pb (Fe _{l / 3} Sb _2/3 ) O ₃

Pb (Fe ₁ Z ₃ Nb ₂ Z ₃ ) O ₃ -PbTiO ₃ -PbZrO ₃ (No. 9, 21, 22, 25 and 32 of Table 2),

Room temperature was used instead of 100 ^° C., while room temperature and 40 kV / cm DC voltage were used for those bodies which contained more than 30 mol percent of the same component (Nos. 17 and 26 of Table 2).

After the ceramic disks had stayed for 24 hours, the electromechanical coupling factor for radial vibrations (k _r ) and the mechanical quality factor (Q _m ) were measured in order to assess the piezoelectric activities. The measurement of these piezoelectric properties was made according to the IRE standard circuit. The value of k _r wurds by the method of comparing the response calculated by the anti-resonant frequency. The dielectric constant (ε) and the dielectric loss factor (tan δ) were also measured at a frequency of 1 KHz.

Tables 1, 2 and 3 show typical results that were obtained. In the tables, the bodies are arranged according to the content of lead titanate ao (PbTiO ₃ ), and some values are also listed for the Curie temperature, which was determined by measuring the temperature change of the dielectric constant (ε). The new connections of the bodies according to Tables 1 and 2 are indicated by black dots in FIGS. 1 and 4, respectively, while the usual connections of the bodies of Table 3 are indicated by crosses in the same figures.

The comparison of the results for the bodies No. 14 and 17 of Table 1 or 10 and 11 of Table 2 with those for the body No. 4 of Table 3 shows that the greatest & _r -value of the new ceramics of this invention is substantially greater maximum Ar value of the common lead titanate-zirconate ceramics, which have hitherto been known as the best piezoelectric ceramic materials. In addition, a comparison of the results in Table 1 or 2 with those in Table 3, in particular between the new and conventional ceramics, in which the proportions of the proportions of lead titanate (PbTiO ₃ ) and lead zirconate (PbZrO ₃ ) are similar, that the ceramics according to the present invention show a remarkably improved y value. This last-mentioned circumstance can be seen even more clearly from FIGS. 2 or 5, in which the solid lines represent the kr values of the new ceramics, the 5 mole percent

Kind only those whose composition is by dis formula

(Pb (Fe ₁ Z ₃ Z ₂ Z ₃ ) O ₃ ) * (PbTiOg) ₂ , PbZrO ₃ ) G.

in which x, y and ζ represent a combination of molar fractions and χ + y + ζ = 1.00, where Z denotes one of the elements niobium (Nb) and antimony (Sb), in the range ABCDEFGHI of FIG . 1 of the drawings is in the case that niobium (Nb) is selected as Z, and is within the range JKLMNO of FIG . 4 of the drawing is for the case that antimony (Sb) is selected for Z. The compilations of the mole fractions of the corner points of each area are as follows:

X y Z A. 0.01 0.55 0.44 B. O ₅ Ol 0.09 0.90 C. 0.10 0.00 0.90 D. 0.40 0.00 0.60 E. 0.50 0.10 0.40 F. 0.50 0.30 0.20 G 0.20 0.65 0.15 H 0.10 0.75 0.15 I. 0.05 0.75 0.20 J 0.01 0.55 0.44 K 0.01 0.09 0.90 L. 0.10 0.00 0.90 M. 0.40 0.00 0.60 N 0.40 0.40 0.20 O 0.05 0.75 0.20

In the event that the share of

Pb (Fe ₁ Z ₂ Z ₃ Nb ₃₎ O ₃ or Pb (Fe _{l / 3} Sb _2/3) O ₃

is less than that falling in the above range, it becomes impossible to sinter in the Complete the manufacture of the ceramics, and also "are the piezoelectric activities of the ceramics obtained are worse than or almost the same as those of the usual lead titanate-zirconate ceramics or, if they are improved, they are insufficient for practical use. is the proportion of

Pb (Fe ₁ Z ₃ Z ₂ Z ₃ ) O ₃

(Fig. 2) or

Pb (Fe ₁ Z ₃ Nb ₂ Z ₃ ) O ₃

Pb (Fe ₁ Z ₃ Sb ₂ Z ₃ ) O ₃

(Fig. 5) and _{contain different proportions of PbTiO 3} and corresponding additional proportions of PbZrO ₃ , while the faint lines show the kr values of a conventional lead-titanate-zirconate ceramic with the different proportions y of PbTiO ₃ .

As can be seen from the foregoing, the present invention provides excellent useful piezoelectric ones Ceramics that have high piezoelectric activities.

From the new ceramics of the ternary system

Pb (Fe ₁ Z ₃ Z ₂ Z ₃ ) O ₃ -PbTiO ₃ -PbZrO ₃

(with Z = Nb or Sb) of this invention achieve the high piezoelectric activities of the above (with Z = Nb or Sb) greater than that falling within the above range, the sintering is difficult to carry out and these three are uniformly solved Components not get with. the result that the piezoelectric activities. of ceramics are so changed that practical use is impossible. Where the proportion of PbTiO ₃ . is outside the specified range, it is difficult to sinter dense ceramic bodies and the product has no practical piezoelectric.! Activities. Finally, if the proportion of PbZrO ₃ does not fall within the specified range, the result is unusable piezoelectric ceramics which have greatly impaired piezoelectric activities. In view of this, it is necessary that the ceramics according to the invention should have compositional proportions such that they fall within one of the above specified ranges when application for practical use is required. The ceramics of these effective compounds show

109 514/328

ίο

have excellent piezoelectric activities and have high Curie temperatures, as shown in the tables 1 and 2 is indicated so that the piezoelectric activities are not lost up to high temperatures. The ternary system

Pb (Fe ₁₇₃ Nb ₂ Z ₃ ) O ₃ or Pb (Fe ₁ Z ₃ Sb ₂ Z ₃ ) O ₃

with PbTiO ₃ and PbZrO ₃ according to the invention exists as a solid solution in a large part of connec- ίο fertilize; such a solid solution has the crystal structure of perovskites. The F i g. 3 and 6 show the crystalline phases of the ceramic compounds which are in the area ABCDEFGHI of FIG . 1 or JKLMNO ^ of F i g. 4, the crystalline phases being determined at room temperature by the powder method of X-ray analysis. These compounds have a perovskite structure with either a tetragonal lattice (indicated by "T" in the figures) or a rhomboetric lattice ao [rhombohedral phase] (indicated by "i?"). The morphotropic phase boundary is indicated by a thick line in each figure. In general, the value for k _{r is} greatest in the area of this phase boundary.

It is evident that the starting materials which are used in the manufacture of the ceramics according to the invention need not only be those which were used in the examples given. In particular, instead of the respective starting materials in the above examples, those oxides can be used which readily decompose at elevated temperatures to form the required compounds, as is the case, for example, with Pb ₃ O ₄ for PbO in the examples. Likewise, salts such as oxalates (e.g. FeC ₂ O ₄ instead of FeO in the examples) or carbonates can be used in place of the oxides given in the examples, which can easily be decomposed into the respective oxides at elevated temperatures. On the other hand, hydroxides of the same character as indicated, e.g. B. Nb (OH) can be used instead of oxides, such as, for example, Nb ₈ O ^. In addition, excellent piezoelectric ceramic materials, which have similar properties to the above-mentioned examples, can also be obtained by using powdered materials of

Pb (Fe _{l / 3} Nb _2/3 ) O ₃ or Pb (Fe _{l / 3} Sb _2/3 ) O ₃ ,
PbTiO ₃ and PbZrO ₃

are first produced and these are used as starting materials to be mixed with one another, be used/

It is common that niobium (V) oxide (Nb ₂ O _? ) And zirconium dioxide (ZrO ₂ ), which are commercially available, each contain a few percent of tantalum (V) oxide (Ta ₂ O ₅ ) and hafnium dioxide (HfO ₂ ) included. Consequently, it is therefore also possible that the ceramic compounds according to the invention contain small amounts of these oxides or elements which are present in the commercially available materials. Moreover, it is even likely that the addition of small amounts of some additional substances to the ceramic compounds of this invention can bring about a further improvement in the piezoelectric properties, similar to the fact known from conventional lead titanate-zirconate ceramics. It is to be understood that the ceramic compounds of this invention may contain suitable additives.

While so far has been described what are presently believed to be advantageous examples of this invention It should also be noted that it is understood that various modifications have been made without departing from the inventive concept, and that this invention covers all ceramic compounds mentioned in the following claims.

Mole fractions of the composition PbTiO ₃ PbZrO ₃ Table 1 Sqm ε ♦ JS Curie- Pb (Fei _{/ 3} Nb ₂ , 3) O3 y Z j tan ο temperature No. X 0.75 0.20 Kr 210 280 (7o) ( ⁰ Q 0.05 0.75 0.15 ( ⁰ Io) 160 270 2.2 1 0.10 0.70 0.25 11th 340 320 4.3 2 0.05 0.70 0.20 8th 200 330 2.1 3 0.10 0.65 0.15 22nd 290 380 3.9 4th 0.20 0.55 0.44 20th 130 470 5.3 5 0.01 0.55 0.40 17th 170 590 1.9 6th 0.05 0.48 0.51 18th 105 1310 2.0 7 ** 0.01 0.48 0.47 35 100 1150 2.4 8th 0.05 0.48 0.42 52 120 880 2.1 9 0.10 0.48 0.32 53 180 740 2.1 10 * 0.20 0.48 0.22 39 140 540 2.1 11th 0.30 0.47 0.51 36 90 1510 6.7 12 * 0.02 0.46 0.49 . 21 90 1695 2.7 13th 0.05 0.46 0.44 65 100 960 2.5 370 14th 0.10 0.43 0.52 68 90 720 2.7 15th 0.05 0.43 0.47 47 85 1600 2.8 16 * 0.10 0.43 0.37 65 130 1220 2.5 340 17th 0.20 0.40 0.50 66 85 600 3.0 18th 0.10 0.40 0.20 44 90 720 2.5 19th 0.40 0.38 0.42 53 95 1780 8.5 20th 0.20 0.33 0.62 14th 160 490 2.7 285 21 0.05 0.33 0.47 58 105 820 3.4 22nd 0.20 42 3.7 23 ** 54

Table 1 continued

No. X y Z k _r Sqm ε tan <5 Curie-
Temperature 24 0.30 0.33 0.37 28 95 1520 5.6 245 25th 0.50 0.30 0.20 10 170 760 11.7 26th 0.50 0.23 0.27 17th 160 1270 8.4 27 0.05 0.20 0.75 25th 300 340 4.2 28 0.10 0.10 0.80 18th 410 400 3.8 29 0.50 0.10 0.40 7th 220 670 12.4 30th 0.01 0.09 0.90 17th 340 260 5.4 31 0.05 0.05 0.90 11th 390 270 4.3 32 0.20 0.05 0.75 21 370 530 3.8 33 0.40 0.05 0.55 11th 350 575 4.3 34 0.10 0.00 0.90 12th 500 400 4.0 35 0.30 0.00 0.70 12th 450 - 540 3.8 36 0.40 0.00 0.60 8th 260 550 4.1

Table 2

Molar fractions of the composition PbTiO ₃ PbZrO ₃ k _r Sqm ε tan <5 Curie- No. Pb (Fe _{] / 3} Sb2 / 3) O3 y Z (%) (%) temperature X ': 0.75 0.20 8th 180 260 1.8 ( ⁰ C) 1 0.05 0.70 0.25 25th 330 320 1.2 2 0.05 0.70 0.20 12th 130 325 1.4 3 0.10 0.55 0.44 22nd 140 440 1.7 4th 0.01 0.55 0.40 43 160 710 1.9 5 ** 0.05 0.48 0.47 65 100 1550 2.3 6th 0.05 0.48 0.42 50 130 1330 2.2 7 * 0.10 0.48 0.32 16 190 580 2.3 8th 0.20 0.48 0.22 10 270 380 5.2 9 * 0.30 0.47 0.51 77 95 1360 2.7 10 0.02 0.46 0.49 77 83 1480 2.8 11th 0.05 0.46 0.44 55 105 1520 2.6 325 12th 0.10 0.43 0.52 65 90 790 3.8 13th 0.05 0.43 0.47 60 105 1250 3.3 14 ** 0.10 0.43 0.37 27 140 860 3.4 285 y 15th 0.20 0.40 0.50 53 105 650 4.0 16 0.10 0.40 0.20 17th 90 570 6.8 17th 0.40 0.38 0.42 45 90 1360 4.0 18th 0.20 0.33 0.62 46 130 560 4.1 245 19 * 0.05 0.33 0.47 37 145 820 5.4 20th 0.20 0.33 0.37 26th 150 , 1160 5.5 21 ** 0.30 0.23 0.47 15th 190 1050 7.6 180 22nd 0.30

Continuation of table 2

No. X y Z K Sqm ε tan <5 Curie-
temperature 23 0.05 0.20 0.75 26th 290 410 4.2 24 0.10 0.10 0.80 17th 370 525 3.8 25th 0.30 0.10 0.60 12th 350 950 7.8 26th 0.40 0.10 0.50 11th 80 2820 8.7 27 0.01 0.09 0.90 12th 530 290 3.8 28 0.05 0.05 0.90 12th 420 370 3.0 29 0.15 0.05 0.80 10 390 475 4.0 30th 0.10 0.00 0.90 8th 380 220 5.0 31 0.20 0.00 0.80 6th 370 465 3.9 32 0.30 0.00 0.70 5 270 870 8.6 33 0.40 0.00 0.60 4th 190 2100 8.9

Note: In the manufacture of the bodies whose numbers have an asterisk in _{Tables 1 and 2, Pb 3} O ₄ was used as lead oxide in place of lead monoxide (PbO) as one of the starting materials.

_{Likewise, iron oxalate (FeC 2} O ₄ ), calculated on the basis of iron (II) oxide, was used instead of iron (III) oxide (Fe ₂ O ₃ ) for the bodies with two stars in the number .

Table 3

Mole fractions of PbZrO ₃ 7th Sqm ε tan ο No. composition 0.30 Kr (%) PbTiO ₃ 0.40 ( ⁰ Io) . 340 5.7 1 0.70 0.45 . - 300 2.4 2 0.60 0.52 -. 30th 350 1.3 3 0.55 0.55 8th 250 160 1.6 4th 0.48 0.60 42 290 640 3.0 5 0.45 0.70 38 320 460 3.1 6th 0.40 0.80 30th 380 380 3.3 7th 0.30 0.90 24 470 350 3.3 δ 0.20 15th 580 280 3.4 9 0.10 10

Note: It was not possible to assess the piezoelectric activities for bodies No. 1 and 2.

Claims (6)

Patent claims: 1. Piezoelectric ceramic material containing lead titanate (PbTiO ₃ ) and / or lead zirconate (PbZrO ₃ ), characterized in that the material consists essentially of a solid solution of the components , PbTiO ₃ and PbZrO ₃ consists, where Z represents the elements niobium (Nb) and / or antimony (Sb). . 2. Piezoelectric ceramic material according to claim 1, characterized in that it is in essentially has a composition represented by the formula (PbTiO ₃ ) ^ (PbZrO ₃ ) ₂ 35 is given, where Z represents one of the elements niobium (Nb) or antimony (Sb) and x, y and ζ indicate molar proportions, the sum of which is 1.0 and the amounts of which are within the following limits of the three-component system of the three components: χ = 0.01 to 0.5;
y = 0.00 to 0.75;
ζ = 0.15 to 0.90. 3. Piezoelectric ceramic material according to claim 1 or 2, characterized in that 45. it essentially has a composition represented by the formula (Pb (Fe ₁ Z ₃ Z ₂ Z ₃ ) O ₃ ) * (PbTiOg) ₂ , (PbZrO ₃ ) _z is given, where Z is one of the elements niobium (Nb) or antimony (Sb) and x, y and ζ indicate molar fractions, the sum of which is 1.0, and that the composition with niobium (Nb) as component Z in the range ABCDEFGHI des The three-component system of FIG. 1, or with antimony (Sb) as component Z in the area JKLMNO of the three-component system of FIG. 4, whereby the following values for each, j and ζ apply to the corner points of these areas: X y Z A. 0.01 0.55 0.44 B. 0.01 0.09 0.90 C. 0.10 0.00 0.90 D. 0.40 0.00 0.60 E. 0.50 0.10 0.40 F. 0.50 0.30 0.20 G 0.20 0.65 0.15 H 0.10 0.75 0.15 I. 0.05 0.75 0.20 J 0.01 0.55 0.44 K 0.01 0.09 0.90 L. 0.10 0.00 0.90 M. 0.40 0.00 0.60 N 0.40 0.40 0.20 O 0.50 0.75 0.20 4. Piezoelectric ceramic material according to one of claims 1 to 3, characterized in that that there are per se known additional components that enhance the piezoelectric properties improve, in amounts up to a few percent (up to about 3%). 5. Piezoelectric ceramic material according to one of claims 1 to 4, characterized in that it contains tantalum (V) oxide (Ta ₂ O ₅ ) and / or hafnium dioxide (HfO ₂ ) in amounts of up to a few percent. 6. Use of the piezoelectric ceramic material according to one of claims 1 to 5 for the manufacture of piezoelectric transducers. 1 sheet of drawings